基于螺芴吖啶类衍生物作为单组分电荷存储层的有机场效应晶体管存储器

doi:10.6023/A24090290

摘要/Abstract

本工作设计并合成了以螺芴吖啶为核的两种芳胺类分子SFDBA-DCz和SFDBA-DPA, 并通过溶液加工法将其作为电荷捕获层, 制备了底栅顶接触型有机场效应晶体管(OFET)存储器. 实验结果显示, 基于SFDBA-DCz的OFET存储器件具有更高的迁移率0.35 cm²•V^-1•s^-1和更高的电流开关比2.1×10⁴, 但基于SFDBA-DPA的OFET存储器件具有更加优越的存储窗口. 维持时间为4000 s时, 基于SFDBA-DPA器件和基于SFDBA-DCz器件的开关比分别为10¹和10³. 综合分析结果显示, 基于SFDBA-DCz的OFET存储器件具有比基于SFDBA-DPA器件更好的器件稳定性和耐受性, 但基于SFDBA-DPA的OFET存储器件具有比SFDBA-DCz器件更加优越的存储窗口.

关键词: 螺芴吖啶基材料, OFET存储器, 芳胺小分子材料, 存储窗口

The study involved the design and synthesis of two aromatic amine molecules, SFDBA-DCz and SFDBA-DPA, based on a spiro[acridine-fluorene] core. These molecules were used as charge trapping layers by solution processing to create bottom-gate-top-contact organic field-effect transistor (OFET) memories based on pentacene. Experimental results revealed that the surface of the SFDBA-DPA thin film, when deposited with pentacene, appeared rougher, possibly due to the strong crystallinity of pure SFDBA-DPA films. This led to poor surface hydrophobicity, which hindered pentacene film growth. In contrast, the SFDBA-DCz thin film, also deposited with pentacene, exhibited relatively smooth surfaces, likely attributed to its good film-forming properties. This smooth surface showed better hydrophobicity, which facilitated pentacene film growth. Regarding device performance, the field-effect mobility (μ) for devices based on SFDBA-DPA and SFDBA-DCz were measured at 0.04 cm²•V⁻¹•s⁻¹ and 0.35 cm²•V⁻¹•s⁻¹, respectively, with threshold voltages (V_th) recorded at 1.70 V and –1.76 V. The on/off current ratios (I_on/I_off) were 2.3×10⁴ and 2.1×10⁴, respectively. These results indicated that devices using SFDBA-DCz exhibited higher mobility and a better current on/off ratio. Furthermore, at a write-in time of 1 s and a write-in voltage of –50 V, devices utilizing SFDBA-DPA and SFDBA-DCz displayed optimal hole storage windows of 10.5 V and 6.62 V, respectively. As the write-in time increased, the storage windows for both materials expanded, with SFDBA-DPA consistently offering a storage window approximately 4 V larger than SFDBA-DCz, regardless of the write-in duration. Under a gate electrode voltage (V_DS) of 10 V, a read voltage of –5 V, and a holding time of 4000 s, the on/off ratios for devices using SFDBA-DPA and SFDBA-DCz were 10¹ and 10³, respectively. This indicates that devices based on SFDBA-DPA had a slightly superior on/off ratio compared to those using SFDBA-DCz. A comprehensive analysis demonstrated that devices employing SFDBA-DCz exhibited enhanced stability and tolerance compared to those based on SFDBA-DPA. However, SFDBA-DPA-based devices showed a superior storage window in comparison to SFDBA-DCz devices.

Key words: spiro[acridine-fluorene] based materials, OFET memory, aromatic amine small molecules, storage window

引用此文

李玥, 刘静, 魏颖, 凌海峰, 解令海. 基于螺芴吖啶类衍生物作为单组分电荷存储层的有机场效应晶体管存储器[J]. 化学学报, 2024, 82(12): 1250-1259.

Yue Li, Jing Liu, Ying Wei, Haifeng Ling, Linghai Xie. Organic Field-Effect Transistor Memory Based on Spiro[acridine-fluorene] Derivatives as Single Component Charge Storage Layer[J]. Acta Chimica Sinica, 2024, 82(12): 1250-1259.

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图/表 12

图式1. 化合物SFDBA-DCz和SFDBA-DPA的合成路线

Scheme 1. Synthetic routes of compounds SFDBA-DCz and SFDBA-DPA

图1. SFDBA-DCz和SFDBA-DPA的HOMO、LUMO电子云图及能级分布图

Figure 1. HOMO and LUMO distribution for SFDBA-DCz and SFDBA-DPA and energy level profile

图2. 化合物SFDBA-DCz的(a) DSC图和(c) TGA图; SFDBA-DPA的(b) DSC图和(d) TGA图

Figure 2. (a) DSC and (c) TGA diagram of SFDBA-DCz; (b) DSC and (d) TGA diagram of SFDBA-DPA

图3. 在SiO2/Si衬底上(a) SFDBA-DPA和(c) SFDBA-DCz薄膜的AFM形貌图; 在(b) SFDBA-DPA和(d) SFDBA-DCz表面生长并五苯的AFM形貌图

Figure 3. AFM morphology of (a) SFDBA-DPA and (c) SFDBA-DCz films on SiO2/Si substrates; AFM morphology of pentacene crystallized on (b) SFDBA-DPA and (d) SFDBA-DCz films

图4. (a) 器件结构图; 基于(b) SFDBA-DPA和(c) SFDBA-DCz作为电荷捕获层的两种OFET存储器的转移特性曲线; 基于(d) SFDBA-DPA和(e) SFDBA-DCz作为电荷捕获层的两种OFET存储器的输出特性曲线; 基于(f) SFDBA-DPA和(g) SFDBA-DCz作为电荷捕获层的两种OFET存储器的回滞特性曲线

Figure 4. (a) Device structure diagram; Transfer characteristic curves of two OFET memories based on (b) SFDBA-DPA and (c) SFDBA-DCz as charge trapping layers; Output characteristic curves of two OFET memories based on (d) SFDBA-DPA and (e) SFDBA-DCz as charge trapping layers; The source-drain hysteresis characteristic curves of two types of OFET memory devices based on (f) SFDBA-DPA and (g) SFDBA-DCz as charge trapping layers

	μ/(cm²•V^-1•s^-1)	V_th/V	I_on/I_off
SFDBA-DPA	0.04	1.70	2.3×10³
SFDBA-DCz	0.35	–1.76	2.1×10⁴

表1. 两种OFET存储器的场效应迁移率μ及初始阈值电压Vth以及电流开关比Ion/Ioff

Table 1. Field-effect mobility (μ), threshold voltages (Vth) and on/off current ratios (Ion/Ioff) of two OFET memories

SFDBA-DPA (1)	0.04	0.038	0.037	0.0378	0.09
SFDBA-DCz (2)	0.123	0.095	0.095	0.0952	0.35

表2. 两种OFET存储器的多种条件下的场效应迁移率μ

Table 2. Field-effect mobility (μ) for two OFET memories under various conditions

SFDBA-DPA (1)	0.23	0.26	0.261	0.2636	0.2556
SFDBA-DCz (2)	2.1	7.8	1.7	1.72	4.4

表3. 不同条件下两种OFET存储器的电流开关比Ion/Ioff

Table 3. The Ion/Ioff for two OFET memories under various conditions

图5. 基于SFDBA-DPA (1)和SFDBA-DCz (2)的OFET存储器在多种条件下的场效应迁移率和电流开关比的对比图

Figure 5. Comparison of field effect mobility and current switching ratio of OFET memories based on SFDBA-DPA (1) and SFDBA-DCz (2) under various conditions

图6. 基于(a) SFDBA-DPA和(c) SFDBA-DCz的OFET存储器的电子存储特性曲线; 基于(b) SFDBA-DPA和(d) SFDBA-DCz的OFET存储器的空穴存储特性曲线, 源漏电压为–10 V的时候, 栅级电压范围选定为10~–20 V; 两种OFET存储器的(e) 不同阈值电压下的空穴存储窗口和(f) 不同读写时间下的空穴存储窗口

Figure 6. Electronic storage characteristic curves of OFET memory devices based on (a) SFDBA-DPA and (c) SFDBA-DCz; Hole storage characteristic curves of OFET memory devices based on (b) SFDBA-DPA and (d) SFDBA-DCz, with a source-drain voltage of –10 V, and the gate voltage range selected as 10 to –20 V; (e) The hole storage windows of two types of OFET memories at different threshold voltages and (f) the hole storage windows at different read-write times

图7. 在空穴捕获模式下, 基于(a) SFDBA-DPA和(c) SFDBA-DCz的OFET存储器的维持时间; 基于(b) SFDBA-DPA和(d) SFDBA-DCz的OFET存储器读写擦循环测试

Figure 7. In the hole trapping mode, retention time of OFET memories based on (a) SFDBA-DPA and (c) SFDBA-DCz; Read-write-erase cycling tests of OFET memories based on (b) SFDBA-DPA and (d) SFDBA-DCz

图8. 黑暗条件和光照条件下基于两种材料作为电荷捕获层的OFET存储器的机理图

Figure 8. Mechanism diagrams of OFET memories based on two materials as charge trapping layers under dark conditions and lighting conditions

参考文献 12

[1]	(a) Luo, X.; Boschloo, G.; Kloo, L.; Sun, L.; Xu, B. Acc. Mater. Res. 2024, 5, 220.
	(b) Liu, H.; Liu, Z.; Li, G.; Huang, H.; Zhou, C.; Wang, Z.; Yang, C. Angew. Chem., Int. Ed. 2021, 60, 12376.
	(c) Lin, Z.-Q.; Sun, P.-J.; Tay, Y.-Y.; Liang, J.; Liu, Y.; Shi, N.-E.; Xie, L.-H.; Yi, M.-D.; Qian, Y.; Fan, Q.-L.; Zhang, H.; Hng, H. H.; Ma, J.; Zhang, Q.; Huang, W. ACS Nano 2012, 6, 5309.
	(d) Li, X. Y.; Chen, X.; Hou, P. F.; Wei, Y.; Xie, L. H.; Huang, W. Polymer Bulletin 2023, 36, 1591. (in Chinese)
	(李晓艳, 陈鑫, 侯鹏飞, 魏颖, 解令海, 黄维, 高分子通报, 2023, 36, 1591.)
[2]	(a) Xia, G.; Qu, C.; Zhu, Y.; Ye, J.; Ye, K.; Zhang, Z.; Wang, Y. Angew. Chem., Int. Ed. 2021, 60, 9598.
	(b) Lee, Y. H.; Lee, W.; Lee, T.; Jung, J.; Yoo, S.; Lee, M. H. Chem. Eng. J. 2023, 452, 139387.
	(c) Wang, Y. K.; Yuan, Z. C.; Shi, G. Z.; Li, Y. X.; Li, Q.; Hui, F.; Sun, B. Q.; Jiang, Z. Q.; Liao, L. S. Adv. Funct. Mater. 2016, 26, 1375.
	(d) Chen, X. K.; Tsuchiya, Y.; Ishikawa, Y.; Zhong, C.; Adachi, C.; Brédas, J. L. Adv. Mater. 2017, 29, 1702767.
	(e) Liu, Q. L.; Ren, B. Y.; Sun, Y. G.; Xie, L. H.; Huang, W. Acta Chim. Sinica 2021, 79, 1181. (in Chinese)
	(刘庆琳, 任保轶, 孙亚光, 解令海, 黄维, 化学学报, 2021, 79, 1181.) doi: 10.6023/A21060253
	(f) Ren, B. Y.; Yi, J. C.; Zhong, D. K.; Zhao, Y. Z.; Guo, R. D.; Sheng, Y. G.; Sun, Y. G.; Xie, L. H.; Huang, W. Acta Chim. Sinica 2020, 78, 56. (in Chinese)
	(任保轶, 依建成, 钟道昆, 赵玉志, 郭闰达, 盛永刚, 孙亚光, 解令海, 黄维, 化学学报, 2020, 78, 56.) doi: 10.6023/A19110406
[3]	Huang, W.; Xie, L. H.; Liu, F.; Tang, C.; Hou, X. Y.; Hua, Y. R.; Fan, Q. L. Synfacts 2006, 2006, 0904.
[4]	(a) Wu, Y.; Lou, S. J.; Xu, D. Q.; Zhou, K.; Xu, Z. Y. CN 202210040991. 0 2024.
	(b) Xu, B.; Bi, D.; Hua, Y.; Liu, P.; Cheng, M.; Grätzel, M.; Kloo, L.; Hagfeldt, A.; Sun, L. Energy Environ. Sci. 2016, 9, 873.
	(c) Zhang, C.; Xu, Y.; Xu, Y.; OuYang, M.; Ma, C. A. Acta Phys.-Chim. Sin. 2010, 26, 993. (in Chinese)
	(张诚, 徐宇, 徐意, 欧阳密, 马淳安, 物理化学学报, 2010, 26, 993.)
	(d) Guan, Y. Q.; Song, J.; Sun, W.; Zhang, Q.; Tang, C.; Li, X.; Feng, X. M.; Qian, Y.; Tao, Y. T.; Chen, S. F.; Wang, L. H.; Huang, W. Acta Phys.-Chim. Sin. 2016, 32, 1534. (in Chinese)
	(关玉巧, 宋娟, 孙威, 章琴, 汤超, 李雪, 冯晓苗, 钱妍, 陶友田, 陈淑芬, 汪联辉, 黄维, 物理化学学报, 2016, 32, 1534.)
[5]	(a) Velusamy, A.; Yu, C.-H.; Afraj, S. N.; Lin, C.-C.; Lo, W.-Y.; Yeh, C.-J.; Wu, Y.-W.; Hsieh, H.-C.; Chen, J.; Lee, G.-H.; Tung, S.-H.; Liu, C.-L.; Chen, M.-C.; Facchetti, A. Adv. Sci. 2021, 8, 2002930. pmid: 18362986
	(b) Yu, Y.; Ma, Q.; Ling, H.; Li, W.; Ju, R.; Bian, L.; Shi, N.; Qian, Y.; Yi, M.; Xie, L.; Huang, W. Adv. Funct. Mater. 2019, 29, 1904602. pmid: 18362986
	(c) Tao, J.; Sun, W.; Lu, L. Biosens. Bioelectron. 2022, 216, 114667. pmid: 18362986
	(d) Mas-Torrent, M.; Rovira, C. Chem. Soc. Rev. 2008, 37, 827. doi: 10.1039/b614393h pmid: 18362986
[6]	Sun, C.; Lin, Z.; Xu, W.; Xie, L.; Ling, H.; Chen, M.; Wang, J.; Wei, Y.; Yi, M.; Huang, W. J. Phys. Chem. C 2015, 119, 18014.
[7]	Wang, J.; Wang, X.; Xu, W.-J.; Lin, Z.-Q.; Hu, B.; Xie, L.-H.; Yi, M.-D.; Huang, W. J. Mater. Chem. C 2015, 3, 12436.
[8]	(a) Wu, N.; He, Z. Q.; Xu, M.; Xiao, W. K. Acta Phys.-Chim. Sin. 2014, 30, 1001. (in Chinese)
	(吴楠, 何志群, 许敏, 肖维康, 物理化学学报, 2014, 30, 1001.)
	(b) Wu, Y.; Liu, X.; Liu, J.; Yang, G.; Deng, Y.; Bin, Z.; You, J. J. Am. Chem. Soc. 2024, 146, 15977.
[9]	Xu, W. J. M.S. Thesis, Nanjing University of Posts and Telecommunications, Nanjing, 2016. (in Chinese)
	(徐文娟, 硕士论文, 南京邮电大学, 南京, 2016.)
[10]	(a) Xie, L.; Ling, Q.; Hou, X.-Y.; Huang, W. J. Am. Chem. Soc. 2008, 130, 2120. doi: 10.1021/ja076720o pmid: 18215037
	(b) Gholami, M.; Tykwinski, R. R. Chem. Rev. 2006, 106, 4997. pmid: 18215037
	(c) Xie, L. H.; Hou, X. Y.; Hua, Y. R.; Huang, Y. Q.; Zhao, B. M.; Liu, F.; Peng, B.; Wei, W.; Huang, W. Org. Lett. 2007, 9, 1619. pmid: 18215037
	(d) Xie, L.-H.; Liu, F.; Tang, C.; Hou, X.-Y.; Hua, Y.-R.; Fan, Q.-L.; Huang, W. Org. Lett. 2006, 8, 2787. pmid: 18215037
[11]	Wang, K.; Ling, H.; Bao, Y.; Yang, M.; Yang, Y.; Hussain, M.; Wang, H.; Zhang, L.; Xie, L.-H.; Yi, M.; Huang, W.; Xie, X.; Zhu, J. Adv. Mater. 2018, 30, 1800595.
[12]	(a) Zhang, Y.-X.; Zhang, L.; Cui, L.-S.; Gao, C.-H.; Chen, H.; Li, Q.; Jiang, Z.-Q.; Liao, L.-S. Org. Lett. 2014, 16, 3748.
	(b) Zhou, Y.; Huang, R.; Yao, D.; Zhang, A.; Sun, Y.; Chen, Z.; Zhu, B.; Zheng, Y. Chin. J. Inorg. Chem. 2024, 40, 701. (in Chinese)
	(周永慧, 黄如军, 姚东超, 张艾巍, 孙渝杭, 陈柱君, 朱柏松, 郑佑轩, 无机化学学报, 2024, 40, 701.)